4-methoxy-4-(tert-butyldimethylsiloxy)-2,5-cyclohexadienone | 108534-51-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 4-methoxy-4-(tert-butyldimethylsiloxy)-2,5-cyclohexadienone
• 英文别名: 4-[tert-butyl(dimethyl)silyl]oxy-4-methoxycyclohexa-2,5-dien-1-one
• CAS: 108534-51-6
• 化学式: C₁₃H₂₂O₃Si
• 分子量: 254.401
• InChiKey: KHUYVDLKPGMKRT-UHFFFAOYSA-N

物化性质

• 沸点：
  301.5±42.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.05
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-methoxy-4-(tert-butyldimethylsiloxy)-2,5-cyclohexadienone 在 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 0.16h， 生成 4-(叔丁基二甲基硅氧基)苯酚
  参考文献：
  名称：

  The unusually slow hydrolysis rate of silyl methyl ketals in benzoquinone systems. The question of siloxy stabilization of an adjacent positive charge and stereoelectronic effects on ketal hydrolysis

  摘要：

  DOI：

  10.1021/jo00273a033
• 作为产物：
  描述：

  tert-butyl-dimethyl-(1,4,4-trimethoxycyclohexa-2,5-dien-1-yl)oxysilane 在 溶剂黄146 作用下， 以 水 、 丙酮 为溶剂， 反应 4.0h， 以97%的产率得到4-methoxy-4-(tert-butyldimethylsiloxy)-2,5-cyclohexadienone
  参考文献：
  名称：

  Mixed methyl-silyl ketals of quinones. Their preparation via anodic oxidation and their chemistry

  摘要：

  DOI：

  10.1021/jo00389a023

文献信息

• Double Hetero-Michael Addition of <i>N</i>-Substituted Hydroxylamines to Quinone Monoketals: Synthesis of Bridged Isoxazolidines
  作者：Zhiwei Yin、Jinzhu Zhang、Jing Wu、Che Liu、Kate Sioson、Matthew Devany、Chunhua Hu、Shengping Zheng

  DOI：10.1021/ol401235z

  日期：2013.7.19

  A general synthesis of bridged isoxazolidines from a double hetero-Michael addition of N-substituted hydroxylamines to quinone monoketals has been developed. The different addition order of N-benzylhydroxylamine and N-Boc hydroxylamine is also discussed. Moreover, the various functionalities in the isoxazolidine products allow facile derivatization.

  已经开发了由N-取代的羟胺的双杂-迈克尔加成到醌单缩酮上的桥连的异恶唑烷的一般合成。的不同加入顺序Ñ -benzylhydroxylamine和Ñ -Boc羟胺进行了讨论。而且，异恶唑烷产物中的各种功能性使得容易衍生。
• Synthesis of o-chlorophenols via an unexpected nucleophilic chlorination of quinone monoketals mediated by N,N′-dimethylhydrazine dihydrochloride
  作者：Zhiwei Yin、Jinzhu Zhang、Jing Wu、Riana Green、Sihan Li、Shengping Zheng

  DOI：10.1039/c4ob00391h

  日期：——

  An unexpected nucleophilic chlorination of a quinone monoketal while carrying out a pyrazolidine synthesis has led to a general preparation of multisubstituted phenols. The products are obtained in good to high yields under mild conditions. The bridged pyrazolidines that were the original targets are obtained in the presence of a protic solvent.

  在进行吡唑啉合成时，发生了一次意外的亲核氯化反应，导致了对醌单缩酮的多取代苯酚的一般制备。在温和条件下，产物以良好至高产率获得。在质子溶剂存在下，原本的桥连吡唑啉目标化合物也能得到。
• Oxygenophilic organoaluminium-promoted 1,4-addition of organolithium reagents to quinone monoacetals
  作者：Alan J. Stern、John S. Swenton

  DOI：10.1039/c39880001255

  日期：——

  Complexation of quinone monoacetals with methylaluminium bis-(2,6-di-t-butyl-4-methylphenoxide), followed by addition of organolithium reagents, gives products from 1,4-addition of the organolithium reagent to the quinone monoacetal.

  醌单缩醛与双（2,6-二叔丁基-4-甲基苯氧基）甲基铝的络合，然后加入有机锂试剂，得到有机锂试剂从1,4-加成到醌单缩醛的产物。
• Oxygenophilic organoaluminum-mediated conjugate addition of alkyllithium and Grignard reagents to quinone monoketals and quinol ethers. The directing effect of a methoxy group on the 1,4-addition process
  作者：Alan J. Stern、Jeffrey J. Rohde、John S. Swenton

  DOI：10.1021/jo00279a033

  日期：1989.9
• Intramolecular anodic carbon-carbon bond-forming reactions of oxidized phenol intermediates leading to spirodienones. Structural effects on reactivity and evidence for a phenoxonium ion intermediate
  作者：John S. Swenton、Kenneth Carpenter、Ying Chen、Michael L. Kerns、Gary W. Morrow

  DOI：10.1021/jo00064a017

  日期：1993.6

  Anodic oxidation of 4-phenylphenol in methanol leads to 4-methoxy-4-phenylcyclohexa-2,5-dienones whereas anodic oxidation of 4-(2-alkenylphenyl)-phenols leads to spirocyclic 2,5-cyclohexadienones in competition with methanol addition to the 4-position. Using 4-phenylphenol and (4-(2-propenylphenyl)phenol as model systems, the optimum conditions for solvent addition versus carbon-carbon bond formation have been studied. The yield of the anodic cyclization reaction shows a dramatic dependence on olefin structure. Whereas 4-(2-propenylphenyl)phenol gives the spirocyclic 2,5-cyclohexadienone in high yield, 4-(2-vinylphenyl)phenol affords the analogous product in only 16 % yield. This low yield of intramolecular carbon-carbon bond-forming reactions can be markedly improved if the vinyl substituent is forced closer to the 4-position of the phenol by the buttressing effect of a o-methyl group. Coloumetric studies as well as the oxidation chemistry of a (4-hydroxyphenyl)(2-propenylaryl)methane derivative support the involvement of a phenoxonium ion as the intermediate in these carbon-carbon bond-forming reactions. Finally, non-oxidative generation of a phenoxonium ion by reaction of 4-hydroxy-4-(2-propenylphenyl)2,5-cyclohexadieneone with methanesulfonyl chloride/triethylamine leads to spirodienones related to those isolated in the anodic oxidation chemistry. Although a slightly acidic media is critical for obtaining good yields of spirodienones for the propenyl system, anodic oxidation of the trimethylsilyl derivatives of the phenol allows this reaction to be performed in neutral or slightly basic media.